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A dual-ion accepting vanadium carbide nanowire

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Cite this: Nanoscale, 2020, 12,

cathode integrated with carbon cloths for high
20868 cycling stability†
Sanghee Nam,a Pitchai Thangasamy,a Saewoong Oh,a Manmatha Mahato,a
Nikhil Koratkarb and Il-Kwon Oh *a

Received 23rd July 2020,
Accepted 16th September 2020
DOI: 10.1039/d0nr05478j
rsc.li/nanoscale
Herein, we report vanadium carbide (V8C7) nanowires (NWs) axially grown on carbon cloths (CCs) as a
dual-ion accepting cathode for both lithium (LIBs) and sodium-ion batteries (SIBs). Using a facile hydro-
thermal method, we grew V2O3 NWs on CCs and subsequently reduced them to V8C7 by annealing with
carbon sources under a H2/Ar atmosphere. In striking contrast to V2O5 NW cathodes obtained by anneal-
ing under air, the V8C7 NWs exhibit outstanding cycling stability during 500 cycles, and good rate capa-
bility for both LIBs and SIBs. V8C7 NWs as cathode active materials for LIBs exhibited 203.9 mA h g−1
specific capacity at 0.1 C after 500 cycles, 91.12% cycling retention and a coulombic efficiency of 99.84%.
As cathodes in SIBs, the V8C7 NWs delivered 176.34 mA h g−1 specific capacity at 0.1 C during 300 cycles.
Their defect sites by removal of the oxygen framework in V2O3 NWs have a high surface area (183.27 m2
g−1) and the unique 1D NW structure highly mitigates the volume changes during charge and discharge
showing a superior electrochemical performance. Compared to commercially available cathodes, V8C7
nanowires have very good cycling stability and enhanced electrical conductivity. Moreover, the synergistic
effect with 3D CCs utilized here as a current collector provides a large number of cation-accessible active
sites in conjunction with high electrical conductivity and chemical stability.

Introduction
Transition metal carbides are outstanding materials, applied
in many diverse industries, including electronics, electrocata-
lysts, metallurgy and energy storage devices.1 Among them,
vanadium carbides have high chemical stability, metallic con-
ductivity, high natural abundance and various possible stoichi-
ometries, such as VC, V2C, V4C3, V6C5 and V8C7 according to
their phase diagram.2–4 Vanadium also has a smaller relative
atomic mass than group IVB, VB and VIB metals. With these
properties, vanadium carbides, especially V8C7, are considered
to be potentially valuable materials in various fields of engin-
eering due to their stable structure. The vanadium atoms of
V8C7 NWs with the space group P4332 are situated slightly
a
National Creative Research Initiative for Functionally Antagonistic Nano-
Engineering, Department of Mechanical Engineering, Korea Advanced Institute of
Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon 34141,
Republic of Korea. E-mail: ikoh@kaist.ac.kr
b
Department of Mechanical, Aerospace and Nuclear Engineering, Rensselaer
Polytechnic Institute, 110 8th Street, Troy, NY 12180, USA
† Electronic supplementary information (ESI) available: Detailed chemical reac-
tion during the hydrothermal method and H2 annealing; a table of electrical
conductivity and sheet resistance; optical images of V8C7 NWs and V2O5 NWs; a
charge–discharge plot and cyclic voltammetry of V2O5 NWs; a table of perform-
ances from other vanadium compounds. See DOI: 10.1039/d0nr05478j
away from the face-centered cubic (fcc) positions. The ordered
carbon atoms are arranged in the vacant sites similar to the
Fm3m arrangement of VC1−x.5 Recently, using density func-
tional theory (DFT) calculation it was expected that hybridiz-
ation between the d-orbitals of vanadium and the s- and
p-orbitals of carbon will lead to the d-band structure expan-
sion, resulting in metallic properties, such as high electrical
conductivity, that are comparable to molybdenum carbides
(Mo2C) and tungsten carbides (WC).6–9
Lithium-Ion Batteries (LIBs) are mainly utilized as power
sources for electronics, electronic vehicles and wearable
systems with good cycling stability and high energy. The
specific capacity and energy density of LIBs are highly depen-
dent on the cathode, which has a relatively lower theoretical
capacity than the anode. In addition, cathode materials must
have high electrochemical stability since their reaction poten-
tial is higher than the anode (<1 V). Widely used cathode
materials, for example LiCoO2, LiNiO2, LiFePO4 and LiMn2O4,
have theoretical capacities of 274, 275, 170 and 148 mA h g−1
(160, 170, 160 and 130 mA h g−1 in practical capacity), respect-
ively, which are significantly lower than graphite (372 mA h g−1)
and most other commercially available anode materials.10–15
Cathode materials based on oxides have poor electrical conduc-
tivity, indicating poor cycling stability and rate capability.
Among cathode materials, LiCoO2 and LiNiO2 have high cost,

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Nanoscale
poor thermal and chemical stability, and fast capacity fading.
LiMn2O4 suffers from performance degradation due to the
Jahn–Teller distortion, and causes Mn dissolution into the elec-
trolyte.13 To overcome these disadvantages, various tri-element
layered compounds such as LiNixCoyMn1−x−yO2 (LCNMO) have
been studied which have relatively lower cost than LCO and
higher capacity than LMO. However, a higher Ni content usually
results in a degradation in cycling and thermal stability and
safety; this phenomenon is due to the higher Li and Ni disorder
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in the crystal structure.16,17 As a result, research into developing
new cathode materials that can overcome the aforementioned
challenges is necessary.
Vanadium oxide is a promising cathode material, because it
has several oxidation valence states from 2 to 5, indicating 298
and 442 mA h g−1 of high theoretical capacity for 2 and 3 Li
ions insertion, respectively. However, it also has poor electrical
conductivity (2.5 S cm−1 for V2O3, 102 S cm−1 for VO2 and 10−2
S cm−1 for V2O3), indicating poor cycling stability and rate
performance.18–22 Consequently, other vanadium compound
cathode materials should be studied.
Sodium-Ion Batteries (SIBs) show outstanding potential for
low-cost future batteries, since sodium (Na) has higher abun-
dance and lower cost than lithium (Li), but is chemically
similar to lithium in standard electrode potential.23,24
However, one major obstacle is the lack of a suitable sodium
cathode material due to larger Na+ radius, which results in
much larger volume expansion when Na+ is inserted into the
cathode. The resulting rapid capacity degradation and struc-
tural collapse are issues that still remain to be solved.
Moreover, the Na+ super-ionic conductor Na3V2(PO4)3 (NVP)
has attractive features, and a small surface area accessible by
the electrolyte, resulting in slow Na ion mass transport.25
Herein, we report a novel cathode material comprising V8C7
NWs, synthesized on carbon cloth current collectors via the
hydrothermal method (Scheme 1). Carbon cloths (CCs), which
were utilized as the current collector for the cathode, have a
Scheme 1 Schematic illustration of the synthesis of vanadium carbide
nanowires (V8C7 NWs) via hydrothermal synthesis and the annealing
process under a H2 and Ar (3 : 1) atmosphere.
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unique 3D structure, good electrical conductivity, chemical
stability and abundance of active sites. Synthesizing 1D V8C7
NWs on 3D CCs when compared to commercially available 2D
layered structures provides a large surface area, abundantly
exposed active sites for cations and good electron transport
pathways for both LIB and SIB applications. In addition, the
highly porous and flexible CCs can mitigate the volume expan-
sion by cation intercalation.26–29 So far, there has been no
study to date on the synthesis of vanadium carbide nanowires
via the hydrothermal synthesis, and their use as a cathode for
both LIBs and SIBs. Based on the performance, we expect V8C7
NWs will provide new opportunities to enhance the electro-
chemical performance of cathodes for LIBs and SIBs.
Experimental section
Preparation of V8C7 NWs via hydrothermal synthesis and H2
annealing
V8C7 NWs were synthesized via the hydrothermal method by
the modifications of our previously reported V2O5 NW syn-
thesis30 The CCs were coated with oxygen plasma at 0.3 torr
under air with a power of 50 W for 5 min (COVANCE-1MPR,
Femto Science Inc.). 1.5 g of NH4VO3 (≥99%) and 2.9 g of
C2H2O4 (≥99%) were dissolved with 50 mL of DI water by soni-
cation for 90 min. After that, a Teflon-lined reaction chamber
accommodated the prepared solution and 0.22 g of C6H12N4
(≥99%, Sigma Aldrich). The plasma-coated CCs were soaked in
the final precursor solution and heated in an electric oven at
150 °C for 1 h, then moved to room temperature and cooled
down. After cooling, they were washed with ethanol and kept
in a drier. After drying, the annealing process was carried out
using a tubular furnace at 360 °C under a H2/Ar mixture (3 : 1
ratio) atmosphere to obtain V8C7 NWs. V2O5 NWs can be
obtained by annealing under air at 360 °C for 5 h.
Material characterization
X-ray diffraction (D/MAX-2500, RIGAKU) analysis was carried out
at 40 kV accelerating voltage and 300 mA current. X-ray photo-
electron spectroscopy (Sigma Probe, Thermo VG Scientific) was
performed to further confirm the formation of V8C7 NWs. Raman
spectroscopy (LabRAM HR Evolution Visible_NIR, HORIBA) and
Fourier-transform infrared spectroscopy (Nicolet iS50, thermo
Fisher Scientific Instrument) were performed in the spectral range
of 100 to 3000 cm−1 at 514 nm and ATR IR (400 to 4000 cm−1),
respectively. Electron paramagnetic resonance analysis was
carried out using an EMX/Plus spectrometer at the X-band fre-
quency (9.623 GHz). EPR parameters were as follows; room temp-
erature, 1 mW of microwave power, 100 kHz and 10 G of modu-
lation frequency and amplitude, respectively, and 25 s of sweep
time. To calculate the g-factor, the following equation was used.
hν
g¼ ð1Þ
μ0 B0
where h is the Planck constant (6.626 × 10−34 J s), ν is the micro-
wave frequency, μ0 is the Bohr magneton (9.2740154 × 10–24 J
Nanoscale, 2020, 12, 20868–20874 | 20869

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T−1) and B0 is the magnetic field strength (3433 × 10−4 T). The
observation of the morphologies of the samples was made using
a scanning electron microscope (SU5000, Hitachi) and high-
resolution scanning transmission electron microscope (Titan
cubed G2 60-300, FEI company). Elemental analysis was carried
out by SEM, high-angle annular dark-field (HAADF) TEM energy
dispersive spectroscopy and elemental analysis (FlashSmart,
Thermo Fisher Scientific). The specific surface area was analyzed
using the N2 adsorption method (3Flex, Micromeritics). A four-
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point probe system was employed to measure the electrical con-
ductivity (CMT-100MP, Advanced Instrument Technology).
Electrochemical characterization
V8C7 NWs as the cathode and lithium metal or sodium metal
as the anode were employed. The electrode has 15 mm dia-
meter and 3 mg of active material. Coin-cell type CR2032 was
fabricated in an Ar-filled glove box (GB-G2100AD, GBI).
Polypropylene (Celgard) was utilized as separators. Electrolytes
employed were 1 M LiPF6 in EC : DMC (1 : 1 vol%) and 1 M
NaPF6 in EC : PC (1 : 1 vol%, MTI Korea). Cyclic charge and dis-
charge (WMPG1000, WonATec) were tested in the 2.0–4.0 V
potential window at various current densities. EIS was
implemented with 10 mV RMS in amplitude and the frequency
range of 500 000 Hz to 0.1 Hz. Cyclic voltammetry (CV) and
electrochemical impedance spectroscopy (EIS) were analyzed
using VersaStat3 (Princeton Applied Research).
Results and discussion
V8C7 NWs directly grown on CCs can be clearly shown as
observed by SEM (Fig. 1a–c). Each nanowire has 2 μm length and
140 nm diameter. Energy dispersive spectroscopy (EDS) mapping
of the V8C7 NWs by SEM and elemental analysis is shown in
Fig. S1 and Table S1.† (V: 53.1 at%, C: 38.4 at% and O: 8.5 at%)
After 10 cycles of charge and discharge, the morphological
change of V8C7 NWs was observed. Nanowires show a volume
change by lithium ion intercalation/deintercalation (Fig. S2†).
TEM images of V8C7 NWs at different magnifications were
obtained as shown in Fig. 1d–f. Abundant defects were
Fig. 1 Morphological studies of the V8C7 NWs directly grown on CCs;
(a–c) SEM images, (d and e) HRTEM images and (f ) the lattice-resolved
HRTEM images.
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expected indirectly from the intensity ratio of the defect region
and graphitic region band (ID/IG) of carbon using Raman spec-
troscopy, as illustrated in Fig. 2c. Carbon replaces the spaces
vacated by oxygen atoms during the H2/Ar annealing process.
HAADF TEM EDS mapping of V, C and O is shown in Fig. S3.†
The lattice of V8C7 NWs is clearly shown in Fig. 1f, indicating
that it has high crystallinity. The specific surface area (SSA =
183.27 m2 g−1) of V8C7 NWs directly grown on textured 3D CCs
was determined using the Brunauer–Emmett–Teller (BET) N2
gas adsorption method.
As the typical XRD pattern of V8C7 NWs (Fig. 2a and b), the
reaction involved in this hydrothermal reaction can be
described as follows:
V2 O3 þ ð5  xÞC ! 2VC1x þ 3CO ð2Þ
VC1−x belongs to the space group Fm3 m with a randomly dis-
tributed small amount of carbon vacancies in the VC1−x
lattice. With annealing, the position of the carbon vacancies
can be changed from disordered to ordered, and the space
group Fm3 m crystal structure is also transformed to P4332,31
as in the following equation:
8VC1x þ ð8x  1ÞC ! V8 C7 ð3Þ
The formation of V8C7 NWs under the hydrothermal con-
ditions is described in detail in the ESI.† The XRD patterns
Fig. 2 Material characterization; (a) X-ray diffraction pattern and (b)
after 10 cycles of charge and discharge, (c) Raman spectroscopy, (d)
Fourier-Transform Infrared Spectroscopy compared to V2O5 NWs, (e
and f ) high resolution X-ray photoelectron spectra of V 2p and C 1s of
V8C7 NWs.
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were well-matched to JCPDS card # 89-1096.1 The peaks at
37.2°, 39.8°, 43.3°, 47.2°, 59.8°, 63.2°, 75.2° and 78.5° corres-
pond to the (222), (320), (400), (200), (520), (440), (622) and
(542) facets of V8C7, respectively.32,33 These peaks belong to a
cubic structure with the P4332 space group, indicating a stable
structure, based on the difference in symmetry.2,34–37
The XRD patterns of V8C7 NWs after 10 cycles of charge and
discharge were obtained to confirm the Li and Na ion storage
mechanism (Fig. 2b). Since peak positions after charging and
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Thus, the defective sites in the V8C7 NWs are expected to have
a positive effect, enhancing the performance. The electro-
chemical performance was measured in the potential window
(2.0 to 4.0 V) at various current densities 0.03 (0.1 C), 0.06 (0.3
C), 0.09 (0.5 C), 0.13 (1 C), 0.25 (2 C), 0.63 (4 C), 0.88 (6 C), 1.25
(12 C), 1.88 (20 C), 2.50 (60 C) and 3.75 A g−1 (120 C), and at
0.1 mV s−1 scan rate for cyclic voltammetry (Fig. 3 and 4),
respectively. For the cyclic charge/discharge measurement, the
V8C7 NWs exhibited 303.28 mA h g−1 specific capacity at

discharging were not changed, the cation storage mechanism 33.3 mA g−1 (0.1 C) in the 1st cycle. After an irreversible reac-
of V8C7 NWs is mainly based on intercalation/deintercalation. tion, the formation of a solid-electrolyte interphase (SEI) layer
The peaks at 2θ = 36°, 44.5° and 55° correspond to the remain- at 277.20 mA h g−1 specific capacity was observed in the 5th
ing Li.38,39 Consequently, the d-spacing in the dominant (400) cycle as shown in Fig. 3a. Until the 200th cycle, a stable specific
plane of V8C7 NWs can be calculated using the cubic system capacity was observed, and 91.12% of cycling retention from
spacing equation (1/d2 = h2 + k2 + l2/a2). The calculated the 5th cycle to the 500th cycle was obtained.
d-spacing value was 4.49 Å, which is consistent with previously V8C7 NWs had a relatively low initial capacity compared to
reported values for V8C7. The electrical conductivity was also 440.76 mA h g−1 of V2O5 NWs. However, capacity degradation
obtained using a four-point probe system in comparison with rapidly occurred in the V2O5 NWs due to their high irreversible
other types of V8C7 (Table S2†). The sheet resistance and resis- reaction in the ω-phase (Fig. S6†). The specific capacities of
tivity of the V8C7 NWs were 1.036 Ω sq−1 and 21.78 mΩ cm−1, V8C7 NWs at several current densities are shown in Fig. 3b and
respectively, indicating 6.44 × 103 S m−1 compared to 2139 Ω c, illustrating the rate performance from 0.1 to 120 C. Due to
sq−1 (32.08 mΩ cm−1 and 2.69 S m−1) for the V2O3 NWs. This their high conductivity and structural stability, with the well-
increase of three orders of magnitude in conductivity confirms crystalized space group P4332, excellent rate performance was
the successful transformation of V2O3 NWs to V8C7 NWs after obtained, indicating better tolerance to high current density.
the annealing process. V8C7 NWs also exhibited high capacities of 292.75, 285.54,
To determine structural and chemical changes in the V8C7, 230.34, 207.99, 179.3, 134.97, 114.48, 93.79, 68.55, 51.37 and
Raman spectra were obtained and are shown in Fig. 2c. The 32.27 mA h g−1 at 0.1, 0.3, 0.5, 1, 2, 4, 6, 12, 20, 60 and 120 C,
D-band and G-band of carbon were located at 1359 and
1600 cm−1, respectively. ID/IG was about 1.26, indicating that
the carbon in the obtained V8C7 NWs has defects and shows
intrinsic hybridization from C (sp2) to C (sp3). Two peaks of
the D-band and G-band of V8C7 NWs were also observed by
Fourier-Transform Infrared Spectroscopy (FTIR, Fig. 2d). The
G-band at a wavenumber of 1625 cm−1 indicates strong CvC
stretching and the D-band at 1448 cm−1 means that it has
defect sites on the materials. Most of the carbon atoms are in
the sp3 state and the synthesized material has high activity,
inducing the localization of surface charges onto active defect
sites. The existence of defects on the carbon atoms anchored
on vanadium atoms in the V8C7 NWs has been confirmed by
EPR spectroscopic analysis (Fig. S4†). A typical EPR spectrum
of carbon shows a strong paramagnetic signal with the g-factor
at ca. 200 266, revealing the presence of free/unpaired elec-
trons (2.0016 to 2.0032) in the V8C7 NWs.40 It strongly con-
firms that V8C7 NWs have more structural defects and/or dan-
gling bond centers.
XPS was carried out to observe V 2p and C 1s spectra. In the
V 2p spectra as shown in Fig. 2e, peaks located at 523.45,
515.83, 518.67 and 511.53 eV were assigned to the V 2p 1/2 and
V 2p 3/2 species, respectively. Three peaks at 287, 285 and 284
eV were observed in the deconvoluted C 1s spectra, as shown in
Fig. 2f, corresponding to the C–O bond, V–C bond and C–C Fig. 3 Electrochemical performance for LIBs; (a and b) charge/dis-
charge curves at 0.1 C during the 100th cycle and at different C-rates
bond, respectively. V–C bonds observed in the V8C7 NWs
from 0.1 C to 120 C; (c) rate performance; (d) cycling stability, compar-
demonstrate the successful synthesis of vanadium carbides. ing V8C7 NWs and V2O5 NWs; (e) cyclic voltammetry measurement at a
The electrochemical performance is known to be signifi- scan rate of 0.1 mV s−1; and (f ) electrochemical impedance spec-
cantly enhanced by increasing surface defects and charge.41–43 troscopy and equivalent electrical circuit model (randles circuit).

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Fig. 4 Electrochemical performance for SIBs; (a) charge/discharge
curves at 0.1 C during the 100th cycle; (b) rate capability at different
C-rates from 0.1 C to 60 C; (c) high cycling stability for the 100th cycle,
(d) CV measurement at a scan rate of 0.1 mV s−1; (e) EIS and equivalent
electrical circuit model (Randles circuit) and (f ) comparison with other
candidate materials for LIBs and SIBs.
respectively. The corresponding current densities are summar-
ized in the inset in Fig. 3c. The V8C7 NWs at 33.33 and 50 mA
g−1 current densities are also found to exhibit good cycling
stability for 500 cycles as shown in Fig. 3d.
CV measurement was implemented at 0.1 mV s−1 scan rate
(Fig. 4e). Two peaks were observed at 2.26 and 2.60 V, indicat-
ing reduction and oxidation reactions, respectively. In the
initial cycle, reduction and oxidation peaks were observed at
2.21 and 2.56 V because of the irreversible reaction to form a
SEI layer on the active material surface. After the initial cycle,
CV curves were stable. EIS could obtain the electrochemical
reaction at the V8C7 NW/electrolyte interface and the surface
resistance produced by the migration of cations (Fig. 4f ). The
electrical circuit model matched with the well-established
Randles circuit. In the high frequency, the surface resistance
by Li ion migration was 4.776 Ω. In the medium frequency
region, a semi-circle appeared because of high charge transfer
and constant phase element (CPE) in active materials.
Moreover, a high diffusion rate, indicating low charge transfer
resistance (Rct), was observed in the diffusion-controlled
regime, showing an angle of around 50° in Warburg impe-
dance. For further comparison with other vanadium com-
pounds, the specific capacity, cycle number, capacity fading
per cycle and corresponding current density are summarized
in Table S3.†
For SIB cathodes, 220.90 mA h g−1 specific capacity was
obtained at 0.1 C (20 mA g−1) in the 1st cycle; then after the
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SEI layer formation, the 5th cycle has a reversible capacity of
200.82 mA h g−1, as shown in Fig. 4a. The rate capability and
the corresponding current densities are shown in Fig. 4b.
Excellent structural stability of V8C7 NWs at various current
densities (0.05 C to 60 C) was obtained. The cycling stability at
0.1 C also demonstrated good cycling retention of 93.34%
from the 5th cycle to the 300th cycle (176.30 mA h g−1 as shown
in Fig. 4c).
CV measurement was also conducted at equivalent scan
rate to that of the LIBs. Similar to LIBs, a pair of redox peaks
in the initial cycle was obtained at 2.35 and 2.74 V. After the
irreversible reaction, two redox peaks, corresponding to oxi-
dation and reduction, were observed at 2.86 and 2.43 V,
respectively, as shown in Fig. 4d. The peak position between
LIBs and SIBs is different because of the standard hydrogen
electrode potential difference (Li+ + e− ⇌ Li, E° = −3.04 V vs.
Na+ + e− ⇌ Na, E° = −2.71 V). The surface resistance at a high
frequency has a similar value to that of LIBs (7.023 Ω), and a
low charge transfer resistance in the low frequency region was
observed at an angle of around 40° as shown in Fig. 4e. The
electrical circuit model matched with the Randles circuit.
Compared to the other candidates,25,44–52 shown in Fig. 4f, the
V8C7 NWs had outstanding electrochemical performance in
the range of C-rates from 0.05 C to 6 C.
Conclusions
In summary, axially grown V8C7 NWs were successfully syn-
thesized on CCs and confirmed by structural and morphologi-
cal characterization. As cathode materials for LIBs and SIBs,
the obtained V8C7 NWs showed superior electrochemical per-
formance, a high specific capacity up to 303.28 and 220.90 mA
h g−1, excellent rate stability from 0.05 C to 120 C and good
cycling stability over 500 and 300 cycles, respectively. This out-
standing performance is attributed to several factors, includ-
ing the relatively light weight of V and C, the formation of
active (defect) sites by removal of oxygen atoms during the
annealing step, and the 1D NW structure with high electrical
conductivity. The defect sites have a high surface area and
mitigate the volume changes during charge and discharge.
Moreover, the enhanced electrical conductivity of V8C7 NWs,
which are prepared by reduction of oxygen, greatly enhanced
the cycling stability up to 500 cycles. The synergistic effect
with 3D CC current collectors is also important since it offers
high electrical conductivity and chemical stability and provides
a flexible 3D substrate, which can alleviate the volume expan-
sion by the intercalation of Li and Na ions. The obtained
results clearly demonstrated that V8C7 NWs can be used as
promising cathode materials for potential LIB and SIB
applications.
Conflicts of interest
There are no conflicts to declare.
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Nanoscale
Acknowledgements
This work was supported by the Creative Research Initiative
Program (2015R1A3A2028975) funded by the National
Research Foundation of Korea (NRF).
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